Lithium-ion Battery Anode Including Core-Shell Heterostructure of Silicon Coated Vertically Aligned Carbon Nanofibers

ABSTRACT

A novel hybrid lithium-ion anode material based on coaxially coated Si shells on carbon nanofibers (CNF). The unique cup-stacking graphitic microstructure makes the CNFs an effective Li +  intercalation medium. Highly reversible Li +  intercalation and extraction were observed at high power rates. More importantly, the highly conductive and mechanically stable CNF core optionally supports a coaxially coated amorphous Si shell which has much higher theoretical specific capacity by forming fully lithiated alloy. Addition of surface effect dominant sites in close proximity to the intercalation medium results in a hybrid device that includes advantages of both batteries and capacitors.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is:

-   -   a continuation-in-part of U.S. non-provisional patent        application Ser. No. 13/779,409 filed Feb. 27, 2013 which claims        benefit and priority to U.S. provisional patent application        61/603,833 filed Feb. 27, 2012;    -   a continuation-in-part of U.S. non-provisional patent        application Ser. No. 13/725,969 filed Dec. 21, 2012 which claims        benefit and priority to U.S. provisional patent application        61/578,545 filed Dec. 21, 2011;    -   and claims benefit and priority to U.S. provisional patent        applications:        -   61/667,876 filed Jul. 3, 2012,        -   61/677,317 filed Jul. 30, 2012,        -   61/806,819 filed Mar. 29, 2013, and        -   61/752,437 filed Jan. 14, 2013.            This application is also related to U.S. non-provisional            patent application Ser. Nos. 13/779,472, 13/779,522, and            13/779,571 all filed on Mar. 26, 2013.

The disclosures of all the above provisional and non-provisional patentapplications are hereby incorporated herein by reference.

BACKGROUND

1. Field of the Invention

The invention is in the field of energy storage devices, including butnot limited to batteries, capacitors and fuel cells.

2. Related Art

Rechargeable lithium ion batteries are key electrical energy storagedevices for power supply in portable electronics, power tools, andfuture electric vehicles. Improving the specific energy capacity,charging/discharging speed, and cycling lifetime is critical for theirbroader applications.

In current commercial Li-ion batteries, graphite or other carbonaceousmaterials are used as the anodes which have a theoretical capacity limitat 372 mAh/g by forming fully intercalated LiC₆ compound. In contrast,silicon has a much higher theoretical specific capacity of 4,200 mAh/gby forming fully lithiated alloy Li_(4.4)Si. However, the large volumeexpansion of lithiated Si by up to ˜300-400% causes great structuralstress that in the past inevitably lead to fractures and mechanicalfailure, which significantly limited the lifetime of prior art Sianodes.

SUMMARY

In some embodiments, a power storage device includes a hybrid core-shellNW (nano-wire) architecture in a high-performance Li-ion anode byincorporating an array of vertically aligned carbon nanofibers (VACNFs)coaxially coated with a layer of amorphous silicon. The verticallyaligned CNFs include multiwalled carbon nanotubes (MWCNTs), which areoptionally grown on a Cu substrate using a DC-biased plasma chemicalvapor deposition (PECVD) process. The carbon nanofibers (CNFs) grown bythis method can have a unique interior morphology distinguishing themfrom the hollow structure of common MWCNTs and conventional solid carbonnanofibers. One of the distinguishing characteristics is that these CNFsoptionally consist of a series of bamboo-like nodes across the mostlyhollow central channel. This microstructure can be attributed to a stackof conical graphitic cups discussed further elsewhere herein. In largerlength scale, these PECVD-grown CNFs are typically uniformly alignednormal to the substrate surface and are well separated from each other.They may be without any entanglement or with minimal entanglement, andthus form a brush-like structure referred to as a VACNF array. Thediameter of individual CNFs can be selected to provide desiredmechanical strength so that the VACNF array is robust and can retain itsintegrity through Si deposition and wet electrochemical tests.

Various embodiments of the invention include types of support filamentsother than VACNFs. These support filaments can include, for example,nanowires, carbon sheets or other structures described herein. Otherembodiments do not include any support filaments and use a binderinstead.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a plurality of vertically alignedcarbon nanofibers grown on the substrate, the carbon nanofibersincluding a plurality multi-walled carbon nanotubes; and an electrolyteincluding one or more charge carriers.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a plurality of vertically alignedcarbon nanofibers grown on the substrate; and a layer of intercalationmaterial disposed on the plurality of vertically aligned carbonnanofibers and configured to have a lithium ion storage capacity ofbetween approximately 1,500 and 4,000 mAh per gram of intercalationmaterial.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a plurality of vertically alignedcarbon nanofibers grown on the substrate; and a layer of intercalationmaterial disposed on the plurality of vertically aligned carbonnanofibers and configured such that an ion storage capacity of theintercalation material is approximately the same at charging rates of 1Cand 3C.

Various embodiments of the invention include a method of producing anenergy storage device, the method comprising providing a substrate;growing carbon nanofibers on the substrate, the carbon nonofibers havinga stacked-cone structure; and applying intercalation material to thecarbon nanofibers, the intercalation material being configured forintercalation of charge carriers.

Various embodiments of the invention include an energy storage systemcomprising: an electrolyte including one or more charge carriers; aconductive substrate; a plurality of vertically aligned supportfilaments attached to the substrate; intercalation material disposed oneach of the support filaments and configured to reversibly adsorbmembers of the charge carriers within a bulk of the intercalationmaterial; and a binder disposed on the intercalation material andincluding a plurality of nanoparticles, each of the nanoparticles beingconfigured to provide surface effect dominant sites configured to adsorbmembers of the charge carriers via faradaic interactions on surfaces ofthe nanoparticles.

Various embodiments of the invention include an energy storage systemcomprising: an electrolyte including one or more charge carriers; aconductive substrate; a plurality of support filaments attached to thesubstrate; intercalation material disposed on each of the supportfilaments and configured to reversibly adsorb members of the chargecarriers within a bulk of the intercalation material; and a binderdisposed on the intercalation material and including a plurality ofsurface effect dominant sites configured to catalyze intercalation ofthe charge carriers into the intercalation material.

Various embodiments of the invention include an energy storage systemcomprising: an electrolyte including one or more charge carriers; aconductive substrate; intercalation material configured to reversiblyadsorb members of the charge carriers within a bulk of the intercalationmaterial; and a binder disposed on the intercalation material andincluding a plurality of nanoparticles, each of the nanoparticles beingconfigured to provide surface effect dominant sites configured to donateelectrons to members of the charge carriers via faradaic interactions onsurfaces of the nanoparticles.

Various embodiments of the invention include an energy storage systemcomprising: a cathode; and an anode separated from the cathode by anelectrolyte including one or more charge carriers, the anode comprising,an intercalation material configured to intercalate the charge carriersand to donate electrons to the charge carriers at a first reactionpotential, a plurality of nanoparticles including surface effectdominant sites configured to donate electrons to the charge carriers ata second reaction potential, a absolute difference between the firstreaction potential and the second reaction potential being less than2.4V.

Various embodiments of the invention include a system comprising: meansfor establishing a potential gradient at an anode of a charge storagedevice, the anode including an electrolyte, a plurality of surfaceeffect dominant sites, an intercalation material and a substrate; meansfor receiving a charge carrier of the electrolyte at one of the surfaceeffect dominant sites; means for receiving an electron at the chargecarrier from one of the surface effect dominant sites; and means forreceiving a charge carrier at the intercalation material.

Various embodiments of the invention include a method of producing anenergy storage device, the method comprising: providing a conductivesubstrate; growing support filaments on the substrate; applyingintercalation material to the support nanotibers, the intercalationmaterial being configured for intercalation of charge carriers; andapplying a plurality of surface effect dominant sites in close proximityto the intercalation material.

Various embodiments of the invention include a method of producing ananode, the method comprising: providing a conductive substrate; mixing abinding material, surface effect dominant sites and intercalationmaterial, the surface effect dominant sites being configured to acceptelectrons from charge carriers at a first reaction potential and theintercalation material being configured to accept the charge carriers orelectrons from the charge carriers at a second reaction potential; andapplying the binding material, surface effect dominant sites andintercalation material to the substrate.

Various embodiments of the invention include a method of producing anenergy storage device, the method comprising: providing a conductivesubstrate; providing support filaments; applying intercalation materialto the support filaments, the intercalation material being configuredfor intercalation of charge carriers; and adding surface effect dominantsites to the support filaments.

Various embodiments of the invention include a method of charging acharge storage device, the method comprising establishing a potentialbetween a cathode and an anode of the charge storage device, the chargestorage device including an electrolyte; receiving a first chargecarrier of the electrolyte at a surface effect dominant site of theanode; transferring an electron of the anode to the first chargecarrier; receiving a second charge carrier of the electrolyte at anintercalation material of the anode; and transferring an electron fromthe intercalation material to the second charge carrier.

Various embodiments of the invention include a method of charging acharge storage device, the method comprising: establishing a potentialgradient at an anode of the charge storage device, the anode includingan electrolyte, a plurality of nanoparticles having surface effectdominant sites, an intercalation material and a substrate; receiving afirst charge carrier of the electrolyte at one of the surface effectdominant sites; transferring an electron to the first charge carrierfrom the one of the surface effect dominant sites; receiving a secondcharge carrier at the intercalation material of the anode; andtransferring an electron from the intercalation material to the secondcharge carrier.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a carbon nanofiber, or other supportfilament, connected to the conductive substrate, the carbon nanofiberincluding a plurality of exposed nanoscale edges along the length of thecarbon nanofiber; and an intercalation material configured to form ashell over at least part of the carbon nanofiber.

Various embodiments of the invention include an energy storage system,such as a battery or electrode, comprising a conductive substrate; acarbon nanofiber, or other support filament, connected to the conductivesubstrate, the carbon nanofiber including a plurality of cup-likestructures along the length of the carbon nanofiber; and anintercalation material configured to form a shell over at least part ofthe carbon nanofiber.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a carbon nanofiber, or other supportfilament, connected to the conductive substrate; and an intercalationmaterial configured to form a shell over at least part of the carbonnanofiber, the intercalation material being disposed in a feather-likestructure along a length of the carbon nanofiber.

Various embodiments of the invention include an energy storage systemcomprising a conductive substrate; a carbon nanofiber connected to theconductive substrate; and an intercalation material configured to form ashell over at least part of the carbon nanofiber, the intercalationmaterial being configured such that expansion of the intercalationmaterial is non-delaminating of the intercalation material from thecarbon nanofiber.

Various embodiments of the invention include 29. A method of producingan energy storage device, the method comprising providing a conductivesubstrate; adding carbon nanofibers to the conductive substrate, thecarbon nanofibers each including a plurality of exposed nanoscale edgesalong the length of the carbon nanofiber; and applying intercalationmaterial to the carbon nanofibers, the intercalation material beingconfigured for intercalation of charge carriers.

Various embodiments of the invention include a method of producing anenergy storage device, the method comprising providing a conductivesubstrate; adding carbon nanofibers to the conductive substrate, thecarbon nanofibers each including a plurality of cup-like structuresalong the length of the carbon nanofiber; and applying intercalationmaterial to the carbon nanofibers, the intercalation material beingconfigured for intercalation of charge carriers.

Various embodiments of the invention include a method of producing anenergy storage device, the method comprising providing a conductivesubstrate; adding carbon nanofibers to the conductive substrate; andapplying intercalation material to the carbon nanofibers, theintercalation material being configured for intercalation of chargecarriers, and the intercalation material being disposed in afeather-like structure along a length of the carbon nanofiber.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B illustrate a CNF array comprising a plurality of CNFgrown on a substrate, according to various embodiments of the invention.

FIGS. 2A-2C illustrate a plurality of vertically aligned CNFs indifferent states, according to various embodiments of the invention.

FIGS. 3A-3C illustrate details of a CNF, according to variousembodiments of the invention.

FIG. 4 illustrates a schematic of the stacked-cone structure of a CNF,according to various embodiments of the invention.

FIGS. 5A-5C illustrate an electrochemical characterization of ˜3 μm longCNFs, according to various embodiments of the invention.

FIGS. 6A-6C illustrates scanning electron microscopy images of 3 μm longCNFs, according to various embodiments of the invention.

FIGS. 7A-7C illustrate results obtained using CNFs including a Si layeras Li-ion battery anodes, according to various embodiments of theinvention.

FIG. 8 illustrates how the capacity of a CNF array varies with chargingrate, according to various embodiment of the invention.

FIG. 9 illustrates Raman spectra of CNF arrays, according to variousembodiments of the invention.

FIGS. 10A-10C shows the variation of Li⁺ insertion-extraction capacitiesand the coulombic efficiency over 15 charge-discharge cycles, accordingto various embodiments of the invention.

FIGS. 11A-11C show scanning electron microscopy images of freshlyprepared CNF arrays, according to various embodiments of the invention.

FIG. 11D shows a cross-section of a nanofiber/silicon complex includingmore than one CNF.

FIG. 12 illustrates a carbon nano-fiber array including fibers of 10 umin length, according to various embodiments of the invention.

FIG. 13 illustrates methods of producing CNF arrays and/or CNFs,according to various embodiments of the invention.

FIG. 14A illustrates a CNF including a power enhancement material,according to various embodiments of the invention.

FIG. 14B illustrates detail of the power enhancement materialillustrated in FIG. 14A, according to various embodiments of theinvention.

FIG. 14C illustrates alternative detail of the power enhancementmaterial illustrated in FIG. 14A, according to various embodiments ofthe invention.

FIG. 15 illustrates an electrode surface including a power enhancementmaterial and non-aligned CNFs coated by intercalation material,according to various embodiments of the invention.

FIG. 16 illustrates an electrode surface including power enhancementmaterial, non-aligned CNFs and free intercalation material, according tovarious embodiments of the invention.

FIG. 17 illustrates an electrode surface including intercalationmaterial and power enhancement material, without CNFs, according tovarious embodiments of the invention.

FIG. 18 illustrates an electrode surface including surface effectdominant sites disposed in close proximity to CNFs, according to variousembodiments of the invention.

FIGS. 19 and 20 illustrate electrode surfaces including surface effectdominant sites disposed in close proximity to free intercalationmaterial, according to various embodiments of the invention.

FIG. 21 illustrates methods of assembling an electrode surface,according to various embodiments of the invention.

FIG. 22 illustrates methods of operating a charge storage device,according to various embodiments of the invention.

DETAILED DESCRIPTION

FIGS. 1A and 1B illustrate a CNF Array 100 comprising a plurality of CNF110 grown on a conductive Substrate 105, according to variousembodiments of the invention. In FIG. 1A the CNF Array 100 is shown inthe Li extracted (discharged) state and in FIG. 1B the CNF Array 100 isshown in the Li inserted (charged) state. The CNF 110 in these and otherembodiments discussed herein are optionally vertically aligned. The CNF110 are grown on a Substrate 105 of Cu using a DC-biased plasma chemicalvapor deposition (PECVD) process. As discussed above, the CNFs 110 grownby this method can have a unique morphology that includes a stack ofconical graphitic structures similar to stacked cups or cones or aspiral. This creates a very fine structure that facilitates lithiumintercalation. This structure is referred to here as the “stacked-cone”structure elsewhere herein. In larger length scale, these CNFs 110 aretypically uniformly aligned normal to the substrate surface and are wellseparated from each other. The diameter of individual CNFs can beselected to provide desired mechanical strength so that the CNF Array100 is robust and can retain its integrity through Si deposition and wetelectrochemical cycles. A seed layer is optionally employed for growingCNFs 110 on Substrate 105. In use the CNF Array 100 is placed in contactwith an Electrolyte 125, which can be a solid, or liquid, or acombination solid and liquid, and also including one or more chargecarriers, such as a lithium ion. The CNFs 110 are configured such thatsome of Electrolyte 125 is disposed between CNFs 110 and/or can readySubstrate 105 via gaps between CNFs 110.

The diameter of individual CNFs 110 illustrated in FIGS. 1A and 1B arenominally between 100 and 200 nm, although diameters between 75 and 300nm, or other ranges are possible. CNFs 110 are optionally tapered alongtheir length. The CNFs 110 produced using the techniques discussedherein have excellent electrical conductivity (σ=˜2.5×10⁻⁵ S/m) alongthe axis and do form firm Ohmic contact with Substrate 105. The openspace between the CNFs 110 enables a Silicon Layer 115 to be depositedonto each CNFs to form a gradually thinned coaxial shell with a mass ata Tip 120 of the CNF 110. This design enables the whole Silicon Layer115 to be electrically connected through the CNF 110 and to remain fullyactive during charge-discharge cycling. The expansion that occurs onalloying of lithium with Silicon Layer 115 can be easily accommodated inthe radial direction, e.g. perpendicular to the long dimension of theCNFs 110. The charge and discharge capacity and cycling stability ofnon-Si-coated CNFs 110 and Si-coated CNFs 110 can be compared. Theaddition of Silicon Layer 115 provided a remarkable Li⁺ insertion(charge) capacity up to 3938 mAh/g_(Si) at the C/2 rate and retained1944 mAh/g_(Si) after 110 cylces. This charge/discharge rate and thecorresponding capacity are significantly higher than previousarchitectures using Si nanowires or hybrid Si—C nanostructures. FIGS. 1Aand 1B are perspective views.

In various embodiments, from 0.01 up to 0.5, 1.0, 1.5, 2.5, 3.0, 4.0,10, 20, 25 μm (or more) nominal Si thickness can be deposited onto 3 μmlong CNFs 110 to form CNF Arrays 100 such as those illustrated in FIGS.1A and 1B. Likewise, in various embodiments, from 0.01 up 0.5, 1.0, 1.5,2.5, 3.0, 4.0, 10, 20, 25 μm (or more) nominal Si thickness can bedeposited onto 10 μm long CNFs 110 to form CNF Arrays 100. In someembodiments, the nominal thickness of Si is between 0.01 μm and the meandistance between CNFs 110.

Using CNF Arrays 100, Li ion storage with up to ˜4,000 mAh/gmass-specific capacity at C/2 rate is achieved. This capacity issignificantly higher than those obtained with Si nanowires alone orother Si-nanostructured carbon hybrids at the same power rate. Theimproved performance is attributed to the fully activated Si shell dueto effective charge collection by CNFs 110 and short Li⁺ path length inthis hybrid architecture. Good cycling stability has been demonstratedin over 110 cycles. In various embodiments the storage capacity of Liion storage of CNF Arrays 100 is approximately 750, 1500, 2000, 2500,3000, 3500 or 4000 mAh per gram of Si, or within any range between thesevalues. As used herein, the term “nominal thickness” (of e.g.. Si) isthe amount of Si that would produce a flat layer of Si, of the saidthickness, on Substrate 105. For example, a nominal thickness of Si of1.0 μm is an amount of Si that would result in a 1.0 μm thick layer ofSi if deposited directly on Substrate 105. Nominal thickness is reportedbecause it can easily be measured by weight using methods know in theart. A nominal thickness of 1.0 μm will result in a smaller thickness ofSi Layer 115 on CNFs 110 because the Si is distributed over the greaterarea of the CNFs 110 surfaces.

FIGS. 2A-2C illustrate CNF Array 100 having an average fiber length ofapproximately 3 μm, according to various embodiments of the invention.FIGS. 2A-2C are scanning electron microscopy (SEM) images. FIG. 2A showsa plurality of vertically aligned CNFs 110 without Silicon Layer 115.FIG. 2B shows a plurality of vertically aligned CNFs 110 includingSilicon Layer 115. FIG. 2C shows a plurality of vertically aligned CNFs110 in the extracted (discharged) state after experiencing 100 lithiumcharge-discharge cycles. The CNFs 110 are firmly attached to a CuSubstrate 105 with essentially uniform vertical alignment and a randomdistribution on the surface of the substrate. The samples used in thisstudy have an average a real density of 1.11×10⁻⁹ CN m Fs/c² (countedfrom top-view SEM images), corresponding to an average nearest-neighbordistance of ˜330 nm. The average length of the CNFs 110 in FIG. 2 is˜3.0 μm with >90% of CNFs in the range of 2.5 to 3.5 μm in length. Thediameter spreads from ˜80 nm to 240 nm with an average of ˜147 nm. Aninverse teardrop shaped Ni catalyst at Tip 120 presents at the tip ofeach CNF 110 capping the hollow channel at the center of the CNF, whichpromoted the tip growth of CNF 110 during the PECVD process. The size ofthe Ni catalyst nanoparticles defined the diameter of each CNFs 110.Longer CNFs 110, up to 10 μm, were also employed in some studies to bediscussed in later sections.

In various embodiments the average nearest neighbor distance can varybetween 200-450 nm, 275-385 nm, 300-360 nm, or the like. Further, theaverage length of the CNFs 110 can be between approximately 2-20, 20-40,40-60, 60-80, 80-100, 100-120, 120-250 (μm), or more. Standard carbonnanotibers as long as a millimeter long are known in the art. In variousembodiments, the average diameter can vary between approximately 50-125,100-200, 125-175 (nm), or other ranges.

An amorphous Si Layer 115 was deposited onto the CNF Array 100 bymagnetron sputtering. The open structure of brush-like CNF Arrays 100made it possible for Si to reach deep down into the array and produceconformal structures between the CNFs 110. As a result, it formed athick Si coating at the CNF tip followed by a gradually thinned coaxialSi shell around the lower portion of the CNF, presenting an interestingtapered core-shell structure similar to a cotton swab. The amount of Sideposition is characterized by the nominal thickness of Si films on aflat surface using a quartz crystal microbalance (QCM) duringsputtering. The Li⁺ insertion/extraction capacities were normalized tothe total Si mass derived from the nominal thickness. At 0.50 μm nominalthickness, the Si-coated CNFs 110 were well-separated from each other,forming an open core-shell CNF array structure (shown in FIG. 2B). Thisstructure allowed electrolyte to freely accessing the entire surface ofthe Si Layer 115. In the embodiment illustrated the average tip diameterwas ˜457 nm in comparison with the ˜147 nm average diameter of the CNFs110 prior to application of the Si Layer 115. The average radial Sithickness at the Tip 120 was estimated to be ˜155 nm. This wasapparently much smaller than the 0.50 μm nominal Si thickness since mostSi spread along the full length of CNFs. Other radial Si thicknesses inthe range of 10-1000, 20-500, 50-250, 100-200 (nm) or different rangesare found in alternative embodiments. As discussed elsewhere herein, thestacked-cone of CNFs 110 provides additional fine structure to the SiLayer 115. The stacked-cone structure is optionally the result of aspiral growth pattern that produces the stacked-cone structure whenviewed in cross-section.

The transmission electron microscopy (TEM) images in FIGS. 3A-3C furtherillustrate the structural details of Si-coated CNFs 110. A Si Layer 115of ˜390 nm Si was produced directly above the Tip 120 of a ˜210 nmdiameter CNF 110. The largest portion of the cotton-swab-shaped Si Layer115 was ˜430 nm in diameter which appeared near the very end of the Tip120. The coaxial Si Layer 115 around the CNF 110 showed a feather-liketexture with modulated contrast, clearly different from the uniform Sideposits above the tip (see FIG. 3A). This is likely a result of thestacked-cone microstructure of the PECVD-grown CNFs 110. It is knownfrom the literature that such CNFs 110 include unevenly stacked cup-likegraphitic structures along the CNF 110 center axis. The use of suchvariations in the diameter of CNFs 110 was previously disclosed incommonly owned U.S. patent application Ser. No. 12/904,113 filed Oct.13, 2010.

The stacked-cone structure along the length of each CNF consists of oneto five, five to fifteen, or more than ten cup-like graphitic layersthat can be clearly seen in FIG. 3B as indicated by the dashed lines. Atthe edge of each stacked-cone the side edges of some of the graphiticlayers are exposed. At these exposed edges lithium may be able topenetrate between the graphitic layers. At a molecular scale, thecup-like structures comprise cones of grapheme and/or graphitic sheetswith which lithium can interact. The cup edges are nanoscale edges andcan have the properties of graphene edges while between the graphiticlayers may be found properties as between graphene sheets. The cup edgesprovide seems in the vertically aligned carbon nano-fibers through whichlithium ions can migrate. The novel microstructure of the VACNFsgenerates stacks of exposed graphitic edges along the length of the CNFsidewall, e.g. the cup edges. These nanoscale edges are similar to theedges typically found on grapheme/graphitic sheets and ribbons. Theseexposed cup edges result in varied silicon nucleation rates and thus amodulated silicon shell texture is produced. These exposed edges alsoform a good interface between the VACNF core and the Si shell tofacilitate fast electron transfer in this hybrid structure. The twodifferent structures of the Si shell can be controlled by varying thegrowth process of the VACNFs. Areas of the VACNF that include the cupstructure results in the feather like Si shell, while areas of the VACNFthat do not include the cup structure have a Si structure similar tothat observed at the tip of the VACNF. The VACNF is optionallyconfigured to have one or more areas without the cup stacking structurealong the length of the VACNFs as well as at the tip. In alternativeembodiments, the carbon nano-fibers still include the cup stackingstructure having exposed graphitic/grapheme or graphite edges but arenot vertically aligned and/or even directly attached to the substrate.While the use of a “cup-stacking” graphitic microstructure is discussedelsewhere herein, other methods of producing exposed nanoscale edges ofgraphite sheets include unzipping carbon nanotubes using an acid.Exposed nanoscale edges produced in this manner are expected to alsoprovide advantages in terms of controlling and/or securing a Si shelland may be included in some embodiments. For example, the edges ofgraphite nanoscale ribbons can be used to influence the growth of a Sishell around these ribbons.

As used herein, the term “nanofiber” is meant to include structurehaving at least two dimensions on the nanoscale (less than onemicrometer). These include, for example, wires, tubes and ribbons inwhich a thickness and width are nanoscale but a length may or may not benanoscale. The term nanofiber is meant to exclude graphene sheets inwhich a thickness may be nanoscale but a length and width are bothnanoscale. In various embodiments the support filaments discussed hereinare nanofibers.

The resolution and contrast of FIGS. 3B and 3C are limited since theelectron beam needs to penetrate through hundreds of nanometer thick CNFor Si-CNF hybrid, but the structural characteristics are consistent withthe high-resolution TEM studies using smaller CNFs in literature. Thisunique structure generated clusters of broken graphitic edges along theCNF sidewall which cause varied nucleation rates during Si depositionand thus modulate the density of the Si Layer 115 on the CNF 110sidewall. The modulated density results in the ultra-high surface areaSi structures indicated by a (100 nm square) Box 310 in FIG. 3A. Thefeather like Si structures of Si Layer 115 provide an excellent Li ioninterface that results in very high Li capacity and also fast electrontransfer to CNF 110. In FIG. 3A the dark area at Tip 120 is Nickelcatalyst for growth of the CNFs. Other catalysts can also be used.

FIGS. 3B and 3C are images recorded before (3B) and after (3C) lithiumintercalation/extraction cycles. The sample in 3C was in the delithiated(discharged) state when it was taken out of an electrochemical cell. Thedashed lines in FIG. 3B are visual guidance of the stacked-cone graphiclayers inside the CNFs 110. The long dashed lines in FIG. 3C representthe sidewall surface of the CNF 110.

As discussed elsewhere herein, the stacked-cone structure of CNFs 110 isdrastically different from commonly used carbon nanotubes (CNTs) orgraphite. The stacked-cone structure results in improved insertion, evenwithout the addition of Si Layer 115, relative to standard carbonnanotubes or nanowires. For example, the stacked-cone graphiticstructure of CNFs 110 allows Li⁺ intercalation into the graphitic layersthrough the sidewall of CNFs 110 (rather than merely at the ends). TheLi+ transport path across the wall of each of CNFs 110 is very shortwith D ˜290 nm in some embodiments), quite different from the long pathfrom the open ends in commonly used seamless carbon nanotubes (CNTs).FIG. 4 illustrates a schematic of the stacked-cone structure of CNFs110. In this particular embodiment the average values of the parametersare: CNF radius r_(CNF)=74 nm, CNF wall thickness t_(w)=˜50 nm,graphitic cone angle θ=10°, and the gaphitic cone lengthD=t_(w)/sinθ=290 nm.

FIGS. 5A-5C illustrate an electrochemical characterization of ˜3 μm longCNFs 110. This characterization illustrates the phenomenon described inrelation to FIG. 4. FIG. 5A shows cyclic voltammograms (CV) from 1.5 Vto 0.001 V versus a Li/Li⁺ reference electrode at 0.1, 0.5 and 1.0 mV/sscan rates. A lithium disk was used as the counter electrode. Data weretaken from the second cycle and normalized to the exposed geometricsurface area. FIG. 5B shows the galvanostatic charge-discharge profilesat C/0.5, C1 and C/2 power rates, corresponding to current densities of647, 323 and 162 mA/g (normalized to estimated carbon mass) or 71.0,35.5 and 17.8 μA/cm2 (normalized to the geometric surface area),respectively. FIG. 5C shows intercalation and extraction capacities (toleft vertical axis) and Coulombic efficiency (to right vertical axis)versus the cycle number at C/1 charge-discharge rate. (The C/1 dischargerate=1 hour, C/2 discharge rate=120 min, 2C=C/0.5=30 min, etc.)

A freshly assembled half-cell typically showed the open circuitpotential (OCP) of the uncoated CNFs 110 anode was ˜2.50 to 3.00 V vs.Li/Li⁺ reference electrode. The CVs measured between 0.001 V and 1.50 Vshow that Li⁺ intercalation starts as the electropotential is below 1.20V. The first cycle from OCP to 0.001 V involved the formation of anecessary protective layer, i.e. the solid electrolyte interphase (SET),by the decomposition of solvent, salts, and impurities and thuspresented a large cathodic current. Subsequent CVs showed smaller butmore stable currents. The cathodic current associated with Li⁺intercalation rose slowly as the electrode potential was swept tonegative until a sharp cathodic peak appeared at 0.18 V. As theelectrode potential was reversed to positive after reaching the lowlimit at 0.001 V, lithium extraction was observed in the whole range upto 1.50 V, indicated by the continuous anodic current and a broad peakat 1.06 V.

The CV features of CNF arrays 100 were somewhat different from those ofstaged intercalation into graphite and slow Li⁺ diffusion into thehollow channel of CNTs. Li-ion insertion into CNFs 110 is likely throughintercalation between graphitic layers from the sidewall due to itsunique structure. The TEM image in FIG. 3C indicates that the graphiticstacks in the stacked-cones inside the CNF 110 are somewhat disruptedduring Li⁺ intercalation-extraction cycles, likely due to the largevolume change that occurs on Li⁺ intercalation. Some debris andnanoparticles are observed as white objects inside CNFs 110 as well asat the exterior surface. These show penetration into the interior of theCNFs through the sidewall.

The galvanostatic charge-discharge profiles in FIG. 5B showed that theLi+ storage capacity decreased as the power rate was increased from C/2to C/0.5 (C/0.5 is also referred to as “2C”). To make it easier tocompare the rates (particularly for those higher than C/1), we use thefractional notation C/0.5 herein instead of “2C” that is more popularlyused in the literature. The Li⁺ intercalation and extraction capacitieswere normalized to the estimated mass of the CNFs 110 (1.1×10⁴ g/cm²)that was calculated based on a hollow vertically aligned CNF structurewith the following average parameters: length (3.0 μm), density (1.1×10⁹CNFs per cm²), outer diameter (147 nm), and hollow inner diameter (49nm, ˜⅓ of the outer diameter). The density of the solid graphitic wallof the CNFs 110 was assumed to be the same as graphite (2.2 g/cm³). Atthe normal C/2 rate, the intercalation capacity was 430 mA h g⁻¹ and theextraction capacity is 390 mA h g⁻¹, both of which are slightly higherthan the theoretical value of 372 mA h g⁻¹ for graphite, which may beattributed to SEI formation and the irreversible Li⁺ insertion into thehollow compartments inside the CNFs 110. The extraction capacities werefound to be more than 90% of the intercalation values at all power ratesand both the intercalation and extraction capacities decreased by ˜9% asthe power rate increased from C/2 to C/1 and by ˜20% from C/1 to C/0.5,comparable to graphite anodes.

Upon charge-discharge cycling, the intercalation capacity was found toslightly drop from 410 mA h g⁻¹ to 370 mA h g¹ after 20 cycles at theC/1 rate, while the extraction capacity was maintained between 375 and355 mA h g⁻¹. The overall coulombic efficiency (i.e. the ratio ofextraction capacity to intercalation capacity) was ˜94%, except in thefirst two cycles due to SEI formation on the CNF 110 surface. The SEIfilm is known to form readily on carbonaceous anodes during the initialcycles which allows lithium ion diffusion but is electricallyinsulating, leading to an increase in series resistance. The TEM image(FIG. 3C) and SEM image (FIG. 6A) show that a non-uniform thin film wasdeposited on the CNF 110 surface during charge-discharge cycles. In someembodiments, the SEI serves as a sheath to increase the mechanicalstrength of the CNFs 110, preventing them from collapsing intomicrobundles by the cohesive capillary force of a solvent as observed inthe study with other polymer coatings.

FIGS. 6A-6C illustrates scanning electron microscopy images of 3μm longCNFs 110, according to various embodiments of the invention. FIG. 6Ashows CNFs 110 in delithiated (discharged) state afterintercalation/extraction cycles. FIG. 6B shows CNFs 110 including SiLayer 115 after 100 cycles in the delithiated state. FIG. 6C shows CNFs110 including Si Layer 115 after 100 cycles in the lithiated state.These images are 45 degree perspective views.

FIGS. 7A-7C illustrate results obtained using CNFs 110 including a SiLayer 115 as Li-ion battery anodes. These results were obtained using anominal Si thickness of 0.50 μm. FIG. 7A shows cyclic voltammogramsbetween 1.5 V and 0.05 V versus Li/Li⁺ at 0.10, 0.50 and 1.0 mV s⁻¹ scanrates. The measurements were made after the sample going through 150charge-discharge cycles and the data of the second cycle at each scanrate are shown. FIG. 7B shows galvanostatic charge-discharge profiles atC/0.5, C/1 and C/2 power rates with the sample at 120 cycles. Allprofiles were taken from the second cycle at each rate. FIG. 7C showsinsertion and extraction capacities (to the left vertical axis) andcoulombic efficiency (to the right vertical axis) of two CNF Arrays 100(used as electrodes) versus the charge-discharge cycle number. The firstCNF Array 100 was first conditioned with one cycle at the C/10 rate, onecycle at the C/5 rate, and two cycles at the C/2 rate. It was thentested at the C/2 insertion rate and C/5 extraction rate for the rest ofthe 96 cycles. The filled and open squares represent the insertion andextraction capacities, respectively. The second electrode was firstconditioned with two cycles each at C/10, C/5, C/2, C/1, C/0.5 and C/0.2rates. It was subsequently tested at the C/1 rate for the next 88cycles. The columbic efficiencies of both electrodes are represented byfilled (1st electrode) and open (2nd electrode) diamonds, which mostlyoverlap at 99%.

The CVs in FIG. 7A present very similar features to those of Sinano-wires. Compared to uncoated CNF Array 110, both the cathodic wavefor Li⁺ insertion and the anodic wave for Li⁺ extraction shift to lowervalues (below ˜0.5 and 0.7 V, respectively). The peak current densityincreases by 10 to 30 times after application of Si Layer 115 and isdirectly proportional to the scan rate. Clearly, alloy-forming Li⁺insertion into Si is much faster than intercalation into uncoated CNFs,which was limited by the slow diffusion of Li⁺ between graphitic layers.The cathodic peak at ˜0.28 V was not observed in previous studies onpure Si nanowires. The three anodic peaks representing thetransformation of the Li—Si alloy into amorphous Si are similar to thosewith Si nanowires despite shifting to lower potentials by 100 to 200 mV.

The galvanostatic charge-discharge profiles of a CNF Array including SiLayer 115, shown in FIG. 7B included two remarkable features: (1) a highLi⁺ insertion (charge) and extraction (discharge) capacity of ˜3000 mA h(g_(Si))⁻¹ was obtained at the C/2 rate even after 120 cycles; and (2)the Li⁺ capacity was nearly the same at the C/2, C/1, and C/0.5 powerrates. In other words, the capacity of CNF Array 100 to operate as anelectrode did not decline when charging rates were increased from C/2 toC/1 and C/0.5. Over these charging rates the capacity was nearlyindependent of charging rate, in various embodiments. The total Li⁺storage capacity of CNF Arrays 100 including Si Layer 115 was about 10times greater than CNF Arrays 100 that lacked Si Layer 115. Thisoccurred even though the low potential limit for the charging cycle wasincreased from 0.001 V to 0.050 V. As a result, the amount of Li⁺intercalation into the CNF core appears to have been negligible. Thespecific capacity was calculated by dividing only the mass of Si thatwas calculated from the measured nominal thickness and a bulk density of2.33 g cm⁻³. This method was chosen as an appropriate metric to comparethe specific capacity of the Si Layer 115 to the theoretical value ofbulk Si. For the 3.0 μm long CNFs 110 deposited with a Si Layer 115 of0.456 μm nominal thickness, the real mass density of Si Layer 115 was˜1.06×10⁻⁴ g cm⁻², comparable to that of CNFs 110 (˜1.1×10⁻⁴ g cm⁻²).The corresponding coulombic efficiency in FIG. 7B is greater than 99% atall three power rates, much higher than that of the CNFs 110 without SiLayer 115.

FIG. 8 illustrates how the capacity of CNF Array 100 varies withcharging rate, according to various embodiments of the invention. Datais shown for several numbers of cycles. FIG. 8 shows average specificdischarge capacity for a group of cycles with identical current ratesversus the charge rate (C-rate) required to achieve full capacity in sethours (C/h e.g., full Capacity/hours). Vertical Lines are focused onC/4, 1C, 3C and 8C. The CNF Array 100 was first conditioned with twocycles each at C/8, C/4, C/2, C/1, C/0.8, C/0.4, and C/0.16 ratessymmetrically, and subsequently tested at a C/1 symmetric rate for thenext 88 cycles. This was repeated from cycle 101 to cycle 200. Startingat cycle 201, the electrode was cycled for five cycles at each of C/4,C/3, C/2, C/1C/0.75, C/0.66, C/0.50, C/0.33, C/0.25, C/0.20 and C/0.15rates symmetrically and subsequently tested at a C/1 symmetric rate forthe next 45 cycles. This was repeated from cycle 301 to cycle 400 andfrom cycle 401 to cycle 500. The change in capacity is small (<16%)while the C-rate is varied by 32 fold. The electrode after 100 cyclesshowed increased capacity when the C-rate is changed from 3C to 8C.Thus, faster charge rates resulted in improved capacity. High capacity(>2,700 mAh/g) was obtained at both high and lower rates (C/4 and 8C).Capacity at rates above 3C increase as C-rate increased. The drop inspecific capacity with the number of cycles is due to known,correctable, factors.

Both the CVs and charge-discharge measurements indicated that the Li⁺insertion into Si Layer 115 was fast and highly reversible, which arefeatures desired for high-performance Li-ion battery anodes. This wasfurther demonstrated (See FIG. 7C) with two long cycling tests on twoidentical samples at different testing conditions: (1) slow asymmetrictests with the C/2 rate for insertion and the C/5 rate for extraction;and (2) the fast symmetric test at the C/1 rate for both insertion andextraction. Both sets of data showed >98% coulombic efficiency over thelong cycling except for the initial conditioning cycles (4 cycles in theformer and 12 cycles in the latter at varied low rates). In the slowasymmetric tests, the insertion capacity only dropped by 8.3% from 3643mA h g⁻¹ at the 5th cycle to 3341 mA h g⁻¹ at the 100th cycle. Even atthe C/1 charge-discharge rate, the insertion capacity only drops by 11%from 3096 mA h g⁻¹ at the 13^(th) cycle to 2752 mA h g⁻¹ at the 100^(th)cycle. The difference in the Li⁺ capacity between these two sets of datawas mostly attributable to the initial conditioning parameters and smallsample-to-sample variations. This was indicated by the similar values ofinsertion-extraction capacity during the first few conditioning cyclesin FIG. 7C at C/10 and C/5 rates. The faster rates (C/0.5 for 9th and10th cycles and C/0.2 for 11th and 12^(th) cycles in sample #2) werefound to be harmful and caused an irreversible drop in the capacity.However, the electrode became stabilized after longer cycling. As shownin FIG. 7B, the charge-discharge profiles are almost identical at C/2,C/1, and C/0.5 rates, which were measured with sample #1 after goingthrough 120 cycles. This is over a charging rate variation of fourtimes.

The specific capacity of the Si Layer 115 in the range of 3000 to 3650mA h g⁻¹ is consistent with the highest values of amorphous Si anodessummarized in literature. It is remarkable that the entire Si shell inthe CNF Array 110 was active for Li+ insertion and remained nearly 90%of the capacity over 120 cycles, which to our knowledge has not beenachieved before except with flat ultrathin (<50 nm) Si films. Thespecific capacity disclosed herein is significantly higher than thosereported using other nanostructured Si materials at similar power rates,including ˜2500 mA h g⁻¹ at the C/2 rate and ˜2200 mA h g⁻¹ at the C/1rate with Si NWs, and ˜800 mA h g⁻¹ at the C/1 rate with randomlyoriented carbon nanofiber-Si core-shell NWs. Clearly, the coaxialcore-shell NW structure on well-separated CNFs 110, such as included invarious embodiments of the invention, provides an enhancedcharge-discharge rate, nearly full Li⁺ storage capacity of Si, and along cycle life, relative to the prior art.

As shown in FIG. 7C, an anomalously high insertion capacity (˜4500 mA hg⁻¹) was always observed in the initial cycles, which was 20-30% higherthan the latter cycles. In contrast, the extraction values wererelatively stable over all cycles. The extra insertion capacity can beattributed to the combination of three irreversible reactions: (1) theformation of a thin SEI (surface electrolyte interphase) layer (of tensof nanometers); (2) reactions of Li with SiO_(x) presented on the Sisurface (SiO_(x)+2×Li→Si+xLi₂O); and (3) the conversion of the startingcrystalline Si coating with a higher theoretical capacity (˜4200 mA hg⁻¹) into amorphous Si with lower capacity (<3800 mA h g⁻¹). The TEMimage (FIG. 3C) and SEM image (FIG. 6B) showed that a non-uniform SEIcan be deposited on the surface of Si Layer 115 after thecharge-discharge cycles. This elastic SEI film can help secure Si Layer115 on the CNF 110 surfaces as CNF Array 110 goes through the largevolume expansion-contraction cycles that occur during thecharge-discharge cycles. The dramatic difference between the SEM imagesin FIGS. 6B and 6C indicates the large expansion of Si Layer 115 in thelithiated (charged) state relative to the non-lithiated state. (Althoughsome of the expansion may be due to oxidation of Li by air as theelectrochemical cell was dissembled for imaging.) Note that theproduction of SEI during initial charge-discharge cycles causes thedifferences seen in Si Layer 115 between FIGS. 3A and 3B. In FIG. 3B theSi has interacted with electrolyte to produce SEI that fills the gapsbetween the feather-like structures. The interaction can include mixing,chemical reactions, charge coupling, encapsulation, and/or the like. TheSi Layer 115, therefore, looks more uniform in FIG. 3B. However, the SiLayer 115 now comprises interleaved layers of Si (the feather-likestructures) and SEI. Each of these interleaved layers can be on theorder of a few 10s of nanometers. The SEI layer can be an ion permeablematerial that is a product of interaction between the electrolyte and SiLayer 115 (or other electrode material).

The crystalline and amorphous structure of the Si shell was revealed byRaman spectroscopy. As shown in FIG. 9, the pristine CNF Array 100including Si Layer 115 showed multiple broad bands overlapped in therange of 350 to 550 cm⁻¹ corresponding to amorphous Si, and a muchhigher sharp band at 480 cm⁻¹ corresponding to nanocrystalline Si. Aftercharge-discharge tests, the sharp peak disappeared while the broad bandsmerged into a single peak at 470 cm⁻¹. The bare CNFs 110 did not showany feature in this range. The crystalline Si peak downshifted by ˜40cm⁻¹ from that measured with a single-crystalline Si(100) wafer and by˜20 to 30 cm⁻¹ from other micro-crystalline Si materials. This shift waslikely due to the much smaller crystal size and large disorders. Theoriginal Si Layer 115 likely consisted of nanocrystals embedded in anamorphous matrix associated with the feather-like TEM image in FIG. 3A.After initial cycles, the Si nanocrystals were converted into amorphousSi, consistent with the TEM images after the cycling test (see FIGS. 3Band 3C). However, the Si Layer 115 apparently did not slide along thelength of the CNF, in contrast to the large longitudinal expansion (byup to 100%) in pure Si NWs. This indicates that, in some embodiments,expansion of the silicon is primarily radial rather than longitudinalwith respect to the carbon nano-fiber. In some embodiments, expansionoccurs between the feather-like structures of the Si. For example, theexpansion of one feather may be in the direction of the nearest neighborfeathers above and below, thus filling the gap between the feathers. Ineither case, the expansion occurs in a manner such that delamination ofthe silicon is dramatically reduced relative to the prior art. Si Layer115 was, thus, securely attached to CNFs 110 for over 120 cycles. Thevolume change of the Si shell during Li insertion was dominated byradial expansion, while the CNF-Si interface remained intact.

Various embodiments of the invention include CNFs 110 having differentlengths and silicon shell thickness. One factor that can be controlledwhen CNFs 110 are generated is the open space between each CNF 110,e.g., the mean distance between CNFs 110 within CNF Array 100. Thisspace allows Si Layer 115 to expand radially when charging and, thus insome embodiments provides stability. Because an optimum electrodestructure depends on both the length of CNFs 110 and the thickness of SiLayer 115, it is sometimes desirable to use longer CNFs 110 and thickerSi Layers 115 in order to obtain higher total Li⁺ storage capacity.Longer CNFs 110 do correlate with greater storage capacity. FIGS.10A-10C shows the variation of Li⁺ insertion-extraction capacities andthe coulombic efficiency over 15 charge-discharge cycles with three 10μm long CNF 110 samples deposited with Si Layer 115 at a nominalthickness of 0.50, 1.5 and 4.0 μm, respectively. After conditioning atthe C/10 rate for the first cycle and the C/5 rate for the second cycle,asymmetric rates (C/2 for insertion and C/5 for extraction) were used insubsequent cycles similar to the measurements of sample #1 in FIG. 7C.This protocol provided nearly 100% coulombic efficiency and minimumdegradation over the cycles. The nominal thickness was measured in situwith a quartz crystal microbalance during sputtering.

The specific capacities as high as 3597 mA h g⁻¹ and 3416 mA h g⁻¹ wereobtained with 0.50 and 1.5 μm thick Si Layer 115, respectively, verysimilar to that with 0.50 μm thick Si Layer 115 on 3.0 μm long CNFs 110(see FIG. 7C). The capacity remained nearly constant over 15 cycles.However, the electrode with 4.0 μm nominal Si thickness showed asignificantly lower specific capacity at only 2221 mA h g⁻¹. Thisindicates that, with expansion, the Si Layers 115 from adjacent CNFs 110began to contact into each other, limiting them from further expansionand limiting diffusion of Li between CNFs 110. As a result, only afraction of the silicon coating was active in lithium insertion. Thecycle stability was correspondingly worse than the samples with thinnerSi Layers 115.

The same amount of Si (500 nm nominal thickness) on CNF Arrays 110comprising 10 μm long CNFs 110 gave nearly the same amount of Li⁺storage capacity (3597 mA h g⁻¹, see FIG. 6 a) as that of 3 μm long CNFs110 (3643 mA h g⁻¹, see FIG. 7C), even though the carbon mass is morethan 3 times higher. This is very strong evidence that the contributionof CNFs 110 is negligible in calculating Li⁺ storage. It is likely thatvery little Li⁺ ions were intercalated into CNFs 110 in the Si-coatedsample, this contributes to the stability of the structure duringmultiple charge-discharge cycles.

The variation of the specific Li⁺ storage capacity in the three samplescorrelated well with their structures revealed by the SEM imagesillustrated in FIGS. 11A-11C. FIGS. 11A-11C show scanning electronmicroscopy images of freshly prepared CNF Arrays 100 (on ˜10 μm longCNFs 110). The Si Layer 115 was generated using a nominal Si thicknessof (a) 0.50 μm, (b) 1.5 μm, and c) 4.0 μm, which were measured in-situusing a quartz crystal microbalance during deposition. All images are45° perspective views. At 0.50 μm nominal Si thickness, the average tipdiameter was found to be ˜388 nm on the 10 μm long CNFs, much smallerthan the ˜457 nm average diameter on the 3.0 μm long CNFs 110. The SiLayer 115 was thinner but more uniformly spread along the 10 μm longCNFs 110.

It is noted that growing 10 μm CNFs 110 took 120 min, about six times aslong as growing the 3 μm CNFs 110. Some nickel catalysts were slowlyetched by NH₃ during the long PECVD process, resulting in continuousreduction in the Ni nanoparticle size and leading to the tapered Tip 120(as shown in FIG. 12). The CNF 110 length variation also increased withlong CNFs 110. These factors collectively reduced the shadow effects ofthe Tip 120. As a result, even at 1.5 μm nominal Si thickness, the CNFs110 coated with Si Layer 115 are well separated from each other. The SEMimage of 1.5 μm Si on 10 μm CNF Arrays 100 (FIG. 11B) is very similar tothat of 0.50 μam Si on 3.0 μm CNF Arrays 110 (FIG. 2B). But as thenominal Si thickness was increased to 4.0 μm, the Si Layers 115 clearlymerged with each other and filled up most of the space between the CNFs110 (see FIG. 10C). This reduced the free space needed to accommodatethe volumetric expansion of the Si Layer 1151. As a result, the specificLi⁺ storage capacity significantly dropped.

FIGS. 11A and 11B each include roughly the same number of CNFs 110,however, in FIG. 11B has substantially fewer visible Tips 120. This isbecause Si Layer 115 can form a nanofiber/silicon complex that includesa single CNF 110 (a cross-section of which is shown in FIG. 1A). Or, SiLayer 115 can form a nanofiber/silicon complex that includes two, threeor more CNF 110 under a single cover of silicon. This occurs when two ormore CNFs 110 come together during the Si Layer 115 deposition process.A nanofiber/silicon complex is a structure that includes a continuous SiLayer 115 that envelops one or more CNF 110. A cross-section of ananofiber/silicon complex that includes two CNF 110 is illustrated inFIG. 11D. In various embodiments at least 1%, 5% or 10% ofnanofiber/silicon complexes include more than one CNF 110.

In various embodiments, instances of CNF Arrays 100 having 0.50 and 1.5μm nominal Si thicknesses have comparable mass-specific capacities of3208±343 and 3212±234 mA h g⁻¹, respectively. The samples with a 4.0 μmnominal Si thickness give much lower capacity at 2072±298 mA h g⁻¹. Thethinner Si coatings are fully activated and provide the maximum Liinsertion capacity that amorphous Si could afford. On the other hand,the area-specific capacity increases proportionally with the Sithickness from 0.373±0.040 mA h cm⁻² at 0.50 μm Si to 1.12±0.08 mA hcm⁻² at 1.5 μm Si thickness, but drops off from the linear curve to give1.93±0.28 mA h cm⁻² at 4.0 μm nominal Si thickness. At the 4.0micrometer nominal silicon thickness, only a fraction of the extrasilicon in the thick Si coating is actively involved in Li storage. Thethickness of 4.0 μm is greater than the mean distance between CNFs 110.The electrochemical results are consistent with the structure shown inSEM image in FIG. 11C, which shows that space between CNFs 110 isessentially filled.

In various embodiments of the invention, the structure of CNF Array 100includes an Si Layer of approximately 200 to 300 nm radial thickness onCNFs 110 having a length of approximately 30-40, 40-75, 75-125 microns(or more or combinations thereof) and diameters on the order of ˜50 nm.In some embodiments, these CNF Array 100 are grown on conductive foilshaving a thickness within the ranges of ˜10 microns, ˜10-20 microns,˜10-50 microns, or more. In various embodiments, Si (equivalent to 1.5μm nominal thickness on a flat surface) is deposited onto 10 μm longCNFs 100 to form CNF Arrays 100. This is accomplished while maintain theopen vertical core-shell nanowire structure with individual CNFs 110well separated from each other such that Li ions can penetrate the CNFArrays 100 between the CNFs 110. This unique hybrid architecture allowedthe Si Layers 115 to freely expand/contract in the radial directionduring Li+ insertion and extraction. High-performance Li storage with amass-specific capacity of 3000 to 3650 mA h g⁻¹ was obtained even at theC/1 rate. The capacity matched the maximum value that would be expectedfrom a similar mass of amorphous Si, indicating that the Si Layer 115was fully active. This 3D nanostructured architecture enables effectiveelectrical connection with bulk quantities of Si material whilemaintaining a short Li+ insertion-extraction path. As a result, highcapacity near the theoretical limit is possible for over 120charge-discharge cycle. There was little change in capacity as the ratewas increased 20 times from C/10 to C/0.5 (or 2C). The high capacity atsignificantly improved charging and power rates and the extraordinarycycle stability make this novel structure a choice anode material forhigh-performance Li-ion batteries. The same core-shell concept may beapplied to cathode materials by replacing the Si shell with TiO₂,LiCoO₂, LiNiO₂, LiMn₂O₄, LiFePO₄, Li₂O, Li₂O₂, or the like.

FIG. 13 illustrates methods of producing the CNF Arrays 100 and/or CNFs110 disclosed herein. In a Provide Substrate Step 1310 a Substrate 105is provided. Substrate 105 is optionally suitable for growth of CNFs110. Substrate 105 may include a variety of materials, for example Cu.Substrate 105 is optionally a conductive foil having a thicknessdescribed elsewhere herein. In an optional Provide Nucleation Sites Step1320 nucleation cites for the growth of CNFs 110 are provided onSubstrate 105. A variety of nucleation materials, such as Ni particles,are known in the art. The nucleation cites are optionally provided at adensity so as to produce mean distances between CNFs 110, such as thosetaught elsewhere herein. Provide Nucleation Sites Step 1320 is optionalin embodiments in which nucleation is not required for growth of CNFs110, or similar structures, or in which CNFs 110 are attached toSubstrate 105 using a binder after being grown elsewhere.

In a Grow CNFs Step 1330 CNFs 110 are grown on Substrate 105 or, in someembodiments separate from Substrate 105. The CNFs 110 are optionallygrown to produce the stacked-cone structure taught elsewhere herein, toproduce structures having exposed graphitic edges along their length, orto produce similarly variable structure. The CNFs 110 can be grown toany of the lengths taught elsewhere herein. Growth is optionallyaccomplished using PECVD processes such as those taught or cited in “Ahigh-performance lithium-ion battery anode based on the core-shellheterostructure of silicon-coated vertically aligned carbon nanofibers”Klankowski et al. J. Mater. Chem. A, 2013, 1, 1055.

In an Apply Si Layer Step 1340 an intercalation material such as SiLayer 115 is applied to the grown CNFs 110. In some embodiments, ApplySi Layer Step 1340 occurs before CNFs 110 are attached to Substrate 105.The applied material may have any of the nominal thicknesses taughtelsewhere herein so as to produce a Si Layer 115 thickness of tens orhundreds of nanometers. In some embodiments, Apply Si Layer Step 1340includes growing intercalation material in structures that are dependenton exposed edges along the lengths of CNFs 110. For example, when CNFs110 include the cup-like structure discussed herein, Apply Si Layer Step1340 includes growing the feather-like structures illustrated in thefigures, e.g. FIG. 3A.

In an optional Apply PEM Step 1345 a power enhancement material (PEM) isadded to the CNF Array 100 or CNFs 110. In some embodiments, Apply PEMStep 1345 occurs before CNFs 110 are attached to Substrate 105. The PEMtypically includes a binder and surface effect dominant sites, asdiscussed in further detail elsewhere herein. In an optional ConditionStep 1350 the CNF Array 100 produced using Steps 1310-1340 isconditioned using one or more lithium intercalation cycles.

FIG. 14A illustrates a CNF 110 including a Power Enhancement Material1320, according to various embodiments of the invention. The PowerEnhancement Material 1320 is applied as a layer over the intercalationmaterial, e.g. over Silicon Layer 115. FIG. 14B illustrates detail ofthe Power Enhancement Material 1320 illustrated in FIG. 14B, accordingto various embodiments of the invention. Power Enhancement Material 1320includes Surface Effect Dominant Sites 1430 and an optional Binder 1440.Silicon Layer 115 is but one example of intercalation material. WhereSilicon Layer 115 is used as an example herein, it should be understoodthat other types of intercalation material can be substituted orcombined with silicon. Such alternative or additional intercalationmaterials include Ag, Al, Bi, C, Se, Sb, Sn and Zn. The CNF 110illustrated in FIG. 14 is typically one of a large number of CNF 110within a CNF Array 100.

In some embodiments, Surface Effect Dominant Sites 1430 include surfacesof a nanoparticle configured to adsorb charge carriers in a faradaicinteraction, e.g., to undergo redox reactions with charge carriers. Theyare referred to as “surface effect dominant” because typically, forthese nanoparticles, the faradaic interaction between the chargecarriers and the nanoparticle surfaces dominate bulk faradaicinteractions. Thus, the charge carriers are much more likely to react atthe surface relative to the bulk of the nanoparticles. For example, alithium ion would more likely adsorb onto the surface of thenanoparticle rather than being absorbed into the bulk of thenanoparticle. These nanoparticle are sometimes referred to as surfaceredox particles. The faradaic interaction results in a pseudo capacitorthat can store a significant amount of loosely bound charge and thusprovide a significant power density. In pseudo capacitance an electronis exchanged (e.g., donated). In this case between the charge carrier tothe nanoparticle. While some potentials would result in someintercalation of charge carrier into the nanoparticle, this does notconstitute the bulk of the interaction at Surface Effect Dominant Sites1430 and can degrade some types of nanoparticles. A faradaic interactionis an interaction in which a charge is transferred (e.g., donated) as aresult of an electrochemical interaction.

The nanoparticles that include Surface Effect Dominant Sites 1430 can becomprised of transition metal oxides, such as TiO₂, Va₂O₅, MnO, MnO₂,NiO, tantalum oxide, ruthenium oxide, rubidium oxide, tin oxide, cobaltoxide, nickel oxide, copper oxide, iron oxide, and/or the like. They mayalso be comprised of metal nitrides, carbon, activated carbon, graphene,graphite, titanate (Li₄Ti₅O₁₂), crystalline silicon, tin, germanium,metal hydrides, iron phosphates, polyaniline, mesophase carbon, and/orthe like. It is appreciated that mixtures of the above and/or othermaterials having desired faradaic properties may be included in theSurface Effect Dominant Sites 1430. In various embodiments, thesenanoparticles can be less than 1, 2, 3, 5, 8, 13, 21 or 34 nanometers indiameter. The lower limit of the nanoparticle size is a function of thesize of the molecules of constituent materials. A nanoparticle includesat least a few molecules. A smaller size provides for a greater surfaceto bulk ratio of possible adsorption sites. However, a particlecomprising only a couple of molecules has reduced stability. Thenanoparticles are optionally multi-layered. For example, they cancomprise a TiO₂ layer (or any of the other nanoparticle materialsdiscussed herein) on a transition metal, Co, Ni, Mn, Ta, Ru, Rb, Ti, Sn,V₂O₂, FeO, Cu or Fe core or a graphene/graphite layer on a core of someother material. In some embodiments, different core materials affect thereaction potentials of the surface material. The amount of SurfaceEffect Dominant Sites 1430 is optionally selected depending on desiredpower and energy densities. For example, a greater power density may beachieved by have a larger number of Surface Effect Dominant Sites 1430per quantity of intercalation material, or a greater amount of energydensity may be achieved by having a larger amount of intercalationmaterial per number of Surface Effect Dominant Sites 1430. It is anadvantage of some embodiments of the invention that both historicallyhigh energy and power density can be achieved simultaneously.

By adsorbing charge carriers on the surface of the nanoparticle thecharge carriers can provide a power density such as previously onlyachieved with capacitors. This is because the release of the charge isnot dependent on diffusion of charge carriers though an intercalationmaterial. Further, by placing the Surface Effect Dominant Sites 1430 inclose proximity to the intercalation material, charge carriers can movefrom the intercalation material to the Surface Effect Dominant Sites1430 (or directly to the electrolyte). This results in energy densitiesthat are equal to or greater than conventional batteries. Both theenergy densities of batteries and the power densities of capacitors areachieved in the same device. Note that during discharge charge carrierswithin the intercalation material can migrate to the Surface EffectDominate Sites 1430 and thus recharge these sites.

In some embodiments, Surface Effect Dominant Sites 1430 are disposed onlarger particles. For example, the particle size may be greater than 1,10, 25, 100 or 250 microns, (but generally less than 1 millimeter).Activated carbon, graphite and graphene are materials that can beincluded in particles of these sizes. For example, activated carbon canbe included in Power Enhancement Material 1320 while having a pore sizeof Surface Effect Dominant Sites 1430 similar to the nanoparticlediameters taught above. For the purposes of this disclosure, ananoparticle is a particle with an average diameter of less than 1 μm.

Optional Binder 1440 is configured to keep the Surface Effect DominantSites 1430 in proximity to the intercalation material. In someembodiments, the distribution of Surface Effect Dominant Sites 1430 isuniform throughout Binder 1440. For example, nanoparticles including theSurface Effect Dominant Sites 1430 may be mixed with Binder 1440 beforeBinder 1440 is applied to the intercalation material to produce arelatively uniform distribution. Alternatively, the nanoparticles may beapplied to the surface of the intercalation material prior toapplication of Binder 1440. This can result in a greater concentrationof Surface Effect Dominant Sites 1430 (within Binder 1440) proximate tothe intercalation material as compared to areas of Binder 1440 that aredistal to the intercalation material. Binder 1440 is optional inembodiments in which Surface Effect Dominant Sites 1430 or theassociated nanoparticles are directly attached to the intercalationmaterial, e.g., attached to Silicon Layer 115.

Binder 1440 is permeable (e.g., porous) to charge carriers of theelectrolyte. Examples of suitable materials for Binder 1440 includepolyvinyl-idene fluoride (PVDF), styrene butadiene rubber, poly (acrylicacid) (PAA), carbo-xymethyl-cellulose (CMC), and/or the like. Otherbinders may be used that meet the permeability requirements. Binder 1440optionally includes materials that increase its conductivity. Forexample, Binder 1440 may include conductive polymer, graphite, graphene,metal nanoparticles, carbon nano-tubes, carbon nano fibers, metalnano-wires, Super-P (conductive carbon black), and/or the like. Thematerials are preferably at concentrations high enough to make Binder1440 conductive, e.g., a percolation threshold.

The addition of Surface Effect Dominant Sites 1430 in close proximity tothe intercalation material (e.g., Silicon Layer 115) does notnecessarily require the use of vertically aligned CNF 110, or anysupport filaments. For example, FIG. 15 illustrates an electrode surfaceincluding Power Enhancement Material 1320 and non-aligned CNFs 110coated by intercalation material, according to various embodiments ofthe invention. In these embodiments, the CNFs 110 are not directlyattached to Substrate 110, but are held in close proximity to Substrate110 by Binder 1440. In some embodiments, CNFs 110 including the cup likestructure illustrated in for example, FIG. 3B. are used in thenon-attached configurations, such as illustrated in FIG. 15. In theseembodiments, the cup-like structure still helps to prevent delaminationof the silicon from the underlying CNF 110. While CNF 110 are usedherein as an example of support filaments, it should be understood thatother types of support filaments discussed herein can be used tosupplement or replace the carbon nanofibers of CNF 110 in any of theexamples.

The embodiments illustrated by FIG. 15 can be produced, for example, byfirst growing unattached CNFs 110. These are then coated with SiliconLayer 115 (or some other intercalation material) such that theintercalation material is generally in contact with the CNFs 110 as acoating layer. The coated CNFs 110 are then mixed with Surface EffectDominant Sites 1430 and Binder 1440. Finally, the resulting mixture isdeposited on Substrate 105.

FIG. 16 illustrates an electrode surface including Power EnhancementMaterial 1320, non-aligned CNFs 110 and free Intercalation Material1610, according to various embodiments of the invention. In theseembodiments, the Intercalation Material 1610 is not necessarily disposedaround the CNF 110 as a coating. The Intercalation Material 1610 is freein the sense that it is not restricted to the surface of CNFs 110,however it is still held in proximity to Substrate 105 by Binder 1440.

The embodiments illustrated in FIG. 16 can be produced, for example, bymixing Binder 1440, Surface Effect Dominant Sites 1430, IntercalationMaterial 1610 and CNF 110 together (in any order). The mixture is thenapplied to Substrate 105. In these embodiments, CNFs 110 may or may notbe attached to Substrate 105 by means other than Binder 1440.Intercalation Material 1610 may and/or may not be in contact with CNF110 or Substrate 105. Likewise, Surface Effect Dominant Sites 1430 areoptionally in contact with Substrate 105, CNF 110 and/or IntercalationMaterial 1610. Intercalation Material 1610 optionally includesparticles, suspensions, clusters, and/or droplets of intercalationmaterial with sizes of at least 0.1, 0.6, 1, 1.5, 2, 3,5, 7, 9, 10, 13,15, 18, 21 or 29 μm or any range there between. Other sizes are possiblein alternative embodiments.

FIG. 17 illustrates an electrode surface including Binder 1440, SurfaceEffect Dominant Sites 1430 and Intercalation Material 1610, withoutsupport filaments, according to various embodiments of the invention. Inthese embodiments Surface Effect Dominant Sites 1430 and IntercalationMaterial 1610 are held in proximity to Substrate 11005 by Binder 1440.

FIG. 18 illustrates an electrode surface similar to that illustrated inFIG. 15. However, in the embodiments illustrated by FIG. 18 SurfaceEffect Dominant Sites 1430 are concentrated in close proximity toIntercalation Material 1610. For example, in some embodiments at least2%, 10%, 25%, 50%, 75% or 85% of Surface Effect Dominant Sites 1430 areon particles in contact with Intercalation Material 1610. Increasedconcentration of Surface Effect Dominant Sites 1430 proximate toIntercalation Material 1610 can be achieved using methods describedelsewhere herein. This results in a greater concentration of SurfaceEffect Dominant Sites 1430 at the surface of Intercalation Material 1610relative to other volumes within Binder 1440.

FIGS. 14C, 19 and 20 illustrate an electrode surface similar to thatillustrated in FIGS. 14B, 16 and 17 respectively. However, in theembodiments illustrated by these figures, Surface Effect Dominant Sites1430 are disposed in close proximity to free intercalation material,according to various embodiments of the invention. As in the embodimentsillustrated by FIG. 18, in some embodiments at least 2%, 10%, 25%, 50%,75% or 85% of Surface Effect Dominant Sites 1430 are in contact withIntercalation Material 1610. In some embodiments a higher concentrationof nanoparticles including Surface Effect Dominant

Sites 1430 are disposed within 5 nanometers of Intercalation Material1610 surfaces than between 10 and 15 nanometers of these surfaces.Increased concentration of Surface Effect Dominant Sites 1430 proximateto Intercalation Material 1610 can be achieved by selecting appropriateZeta potentials of the nanoparticles and Intercalation Material 1610 insolution so that the nanoparticles form an electrostatic double layer atthe surface of Intercalation Material 1610. The Zeta potential is theelectric potential in the interfacial double layer at the location ofthe surface versus a point in the bulk liquid away from the surface. TheZeta potential is optionally greater than 25 mV (absolute). In otherembodiments, the nanoparticles are applied to the surfaces ofIntercalation Material 1610 prior to the application of Binder 1440.

Intercalation Material 1610, as illustrated in FIGS. 16-20, can includeany single one or combination of the materials discussed herein withrespect to Silicon Layer 115 (including or excluding silicon). Likewise,CNFs 110, as illustrated in FIGS. 16-20, can include any single one orcombination of the various types fibers discussed here (including orexcluding carbon nanofibers). For example, these CNFs 110 may includebranched fibers, multi-walled fibers, wires, aerogel, graphite, carbon,graphene, boron-nitride nanotubes, etc. The number of Surface EffectDominant Sites 1430 and CNF 110 shown in these figures and other figuresherein is for illustrative purposes only. For example, in practice thenumber of Surface Effect Dominant Sites 1430 can be much greater.Likewise, the amount and size of Intercalation Material 1610 and SiliconLayer 115 shown s for illustrative purposes. Alternative embodiments mayinclude greater or lesser amounts and greater or lesser sizes. Likewise,the depth of PEM 1420 and the length of CNF 110 can vary from that shownin the figures.

In various embodiments, the amount of nanoparticles including SurfaceEffect Dominant Sites 1430 may be selected to so as to result in atleast 0.1, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 2, 3, 5, 10, 25, 50 or 100 (orany range there between) times a monolayer of the nanoparticles on thesurface of Intercalation Material 1610 or Silicon Layer 115 (as measuredin a discharged state). As used herein, a 0.1 monolayer indicates 10%and a 10× monolayer is 10 monolayers. In various embodiments, the amountof nanoparticles including Surface Effect Dominant Sites 1430 may beselected to result in at least 1, 5, 10, 20, 50, 100, 250 or 500nanometer layer (or any combination there between) of nanoparticles onthe surface of Intercalation Material 1610 (as measured in a dischargedstate). Other coverage densities as measured in monolayers or depth arepossible. As the coverage of the nanoparticles (that include SurfaceEffect Dominant Sites 1430) approaches 1.0 monolayer the nanoparticlescan form a layer between the Intercalation Material 1610 and chargecarriers of the electrolyte that migrate through Binder 1440. Forexample in some embodiments the electrolyte includes lithium as a chargecarrier. The lithium can migrate through Binder 1440 and undergo afaradaic reaction with Surface Effect Dominant Sites 1430 in which anelectron is donated to the lithium from one of Surface Effect DominantSites 1430. This electron has been transferred (e.g., donated) fromSubstrate 105 to the nanoparticle via Intercalation Material 1610.Because the nanoparticles form a barrier, at this stage in a chargingprocess, only a limited amount of charge carrier reaches IntercalationMaterial 1610. Charging is dominated by reactions at the Surface EffectDominant Sites 1430. In some embodiments, charging can be rapid becauseintercalation of the charge carrier into Intercalation Material 1610 isnot necessary before the faradaic reaction with the charge carrieroccurs. The presence of Surface Effect Dominant Sites 1430 geatlyincreases the surface area where the initial faradaic reaction can occurprior to intercalation. Surface Effect Dominant Sites 1430 catalyze theintercalation of charge carrier into Intercalation Material 1610. Thecharge carrier can be intercalated in the form as received at SurfaceEffect Dominant Sites 1430 or intercalated in an alternate form such asa metal oxide. If intercalated as a metal oxide, the oxygen of the oxidemay be recycled back to the Surface Effect Dominant Site 1430 followingthe intercalation.

In some embodiments, because the nanoparticles form an imperfect barriersome charge carriers still reach Intercalation Material 1610 at thisstage of charging (e.g., an initial stage of charging a power storagedevice including the electrodes discussed herein). Because theIntercalation Material 1610 of some embodiments, such as silicon,expands when charge carrier intercalation occurs the surface areaIntercalation Material 1610 also increases. This reduces the surfacecoverage of nanoparticles on the surface of Intercalation Material 1610and reduces the effectiveness of the nanoparticles in forming a barrierto charge carriers. Thus, as charging progresses, greater numbers ofcharge carriers per unit time can reach Intercalation Material 1610.This is optionally continued until charging is dominated by reactionswithin the Intercalation Material 1610. The reduction in surfacecoverage may also increase the average fraction of Surface EffectDominant Sites 1430 on each nanoparticle that are exposed to theelectrolyte. As used herein the phrase “surface coverage” is used torepresent a density of a species on a surface and may be measured as anumber of monolayers (or fraction thereof), as a thickness, or as aconcentration, etc.

In some embodiments, the power storage at Surface Effect Dominant Sites1430 occurs at potentials at which faradaic surface reactions occur butintercalation of charge carriers into the nanoparticles that include theSurface Effect Dominant Sites 1430 does not occur. This preventsdegradation of the nanoparticles by repeated intercalation andde-intercalation of charge carrier and allows for a longer cyclelifetime. At the same electrode it is desirable to store power withinIntercalation Material 1610 via faradaic reactions that occur at ahigher potentials, optionally including potentials that would causeintercalation of charge carriers into the nanoparticles having SurfaceEffect Dominant Sites 1430. This can occur in some embodiments of theinvention because there is a potential drop between Substrate 105 andthe Electrolyte 125.

In one specific example, in which lithium is the charge carrier, theSurface Effect Dominant Sites 1430 are on TiO₂ nanoparticles andIntercalation Material 1610 is predominantly silicon. The particularvoltages in other embodiments will be understood to be dependent on thechemical species included in Surface Effect Dominant Sites 1430 andIntercalation Material 1610, and the reactions occurring duringcharging, etc. In various embodiments the potential difference betweenSurface Effect Dominant Sites 1430 and Substrate 105 is at least 0.001,0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.3, 1.7, 2.0, 2.2, or 2.4V, or anyrange there between. As used herein the term “potential” is used torefer to an absolute value (e.g., |x|) of an electrostatic potential.

FIG. 21 illustrates methods of assembling an electrode surface,according to various embodiments of the invention. The assembledelectrode surface may be used, for example, as an anode in a battery,capacitor or hybrid device. The methods illustrated in FIG. 21 areoptionally used to produce the various electrodes discussed elsewhereherein.

In a Provide Substrate Step 2110 a conductive substrate is provided.Provide Substrate Step 2110 is similar to Provide Substrate Step 1310.In Provide Substrate Step 2110, Substrate 105 optionally suitable forgrowth of CNFs 110 or other support filaments is provided. As discussedherein, Substrate 105 may include a variety of materials, for exampleCu, Au, Sn, etc. Substrate 105 optionally includes nucleation sites asdescribed elsewhere herein.

In an optional Provide CNF Step 2120, CNF 110 (or any of the othersupport filaments described herein) are provided. Provide CNF Step 2120is optional in embodiments in which electrodes that lack supportfilaments, such as those illustrated by FIGS. 17 and 20, are produced.In some embodiments the CNF 110 are provided by growing CNF 110 onSubstrate 105. In some embodiments, CNF 110 are provided by adding CNF110 to a mixture, that is later applied to Substrate 105. In someembodiments CNF 110 are produced separate from Substrate 105 and laterattached to Substrate 105.

In a Provide Intercalation Material Step 2130, Intercalation Material1610 is provided. In some embodiments, Intercalation Material 1610 isfirst applied to CNF 110. In various embodiments, Intercalation Material1610 is applied as a colloidal suspension, using vapor deposition, in asolvent, as a paste, or the like.

In a Provide Surface Effect Dominant Sites (SEDS) Step 2140, SurfaceEffect Dominant Sites 1430 are provided. As discussed elsewhere herein,the Surface Effect Dominant Sites 1430 may be disposed on nanoparticlesor larger structures such as graphite, graphene or activated carbon.Surface Effect Dominant Sites 1430 can be provided as a suspension inBinder 1140, or in a solvent, using sputter deposition, using electrodeposition, using evaporation, as a spray or the like. In someembodiments a Zeta potential of Intercalation Material 1610 is selectedsuch that Surface Effect Dominant Sites 1430 are concentrated atsurfaces of Intercalation Material 1610.

In an Apply Step 2150 Intercalation Material 1610, Surface EffectDominant Sites 1430 and optionally CNFs 110 are applied to Substrate105. These materials can be applied in a wide variety of orders andcombinations. For example, Intercalation Material 1610 can be applied toCNFs 110 (perhaps already attached to Substrate 105) and then SurfaceEffect Dominant Sites 1430 can be then applied on top of theIntercalation Material 1610. Alternatively, free CNF 110, IntercalationMaterial 1610 may be first mixed, then Surface Effect Dominant Sites1430 and Binder 1140 either alone or in combination are added. Based onthe teachings herein, one of ordinary skill in the art will understandthat in different embodiments, these components can be mixed or added inany order or combination. Further, the components can be mixed prior toor after being applied to Substrate 105. The Steps 2110-2150 can beperformed in any order. Apply Step 2150 is optionally followed byCondition Step 1350.

In some embodiments the method illustrated in FIG. 21 includes mixingIntercalation Material 1610 and Surface Effect Dominant Sites 1430 in asuspension in a solvent with a sufficient amount of dispersion. Thedispersion is optionally applied to CNFs 110. The solvent of thedispersion is then evaporated from the mixture resulting in a powder orcoating on the CNFs 110. Binder 1440 can be added to the suspensionbefore or after application to the CNFs 110. In some embodiments, theapplication of Surface Effect Dominant Sites 1430 occurs at the finalstage of Intercalation Material 1610 deposition by changing thematerials being sputtered onto Substrate 105. In these embodiments, forexample, TiO2 can be added to the sputtering mix after almost all theIntercalation Material 1610 is deposited. This produces a sputteredlayer of TiO₂ as Surface Effect Dominant Sites 1430 on top ofIntercalation Material 1610.

FIG. 22 illustrates methods of operating a charge storage device,according to various embodiments of the invention. This method may beused, for example, when charging the charge storage device. In someembodiments the method includes attaching a charging device to both ananode and cathode of the charge storage device via wires. This chargingstorage device places potentials at the anode and cathode resulting in apotential gradient there between. The potential gradient driveselectrons into the anode. The steps illustrated in FIG. 22 optionallyoccur contemporaneously, e.g., they can occur at the same or atoverlapping times with respect to each other.

In an Establish Potential Step 2210 a potential is established at thecharge storage device. This potential may be between an anode and acathode of the charge device. Such a potential will result in apotential gradient between Substrate 105 and Electrolyte 125 within thecharge storage device. The potential gradient can produce a potentialdifference between locations of Surface Effect Dominant Sites 1430 andIntercalation Material 1610. In various embodiments this potentialdifference is at least 0.001, 0.1, 0.3, 0.4, 0.5, 0.8, 1.0, 1.3, 1.7,2.0, or 2.4 V, or any range there between.

In a Receive Lithium Step 2220 a charge carrier, of which Lithium is butone possible example, is received at one of Surface Effect DominantSites 1430. This charge carrier is optionally received through Binder1440.

In a Transfer Electron Step 2230 an electron is transferred (e.g.,donated) from Surface Effect Dominant Site 1430 to the charge carrierreceived in Receive Lithium Step 2220. This transfer may comprisesharing of the electron between the Surface Effect Dominant Site 1430and the charge carrier. The electron is transferred in a faradaicreaction and is typically conducted from Substrate 105. The transferoccurs while the charge carrier is at the surface of the Surface EffectDominant Site 1430 and occurs at the potential of that location. Areaction potential of the electron transfer is, for example, dependenton the reaction potential of the charge carrier and the reactionpotential of the Surface Effect Dominant Site 1430. The reactionpotential can be dependent on both the Surface Effect Dominant Site 1430and the nearby Intercalation Material 1610. As used herein, the term“reaction potential” is used to refer to the potential at which areaction occurs at an appreciable rate. The reaction potential of areaction can be illustrated by, for example, peaks in a cyclicvoltammogram. In another example, the potentials required for thereactions Li⁺+c⁻→Li or 2Li⁺+MO+2e⁻=Li₂O+M (where M is any of thetransition metals discussed herein) to occur in an electrochemical cellare the reaction potentials of these reactions. The reaction potentialcan be highly dependent on the environment in which the reaction occurs.For example, the second reaction above may have a lower reactionpotential in the presence of a TiO₂ nanoparticle having a diameter inthe range of 2-10 nm. Likewise, the reaction potential can be influencedby the energy required for intercalation or by the close proximity ofSurface Effect Dominant Sites 1430 and Intercalation Material 1610.

In an Intercalate Lithium Step 2240 a charge carrier, of which Lithiumis but one possible example, is intercalated within IntercalationMaterial 1610. This step may include migration of the charge carrierinto the bulk interior of Intercalation Material 1610. The chargecarrier can be received at Intercalation Material 1610 as the samechemical species as received at the Surface Effect Dominant Sites 1430in Receive Lithium Step 2220, or alternatively in as a chemical speciesproduced at the Surface Effect Dominant Sites 1430. For example, thecharge carrier can be received at the Intercalation Material 1610 as anoxide (e.g., Li₂O, etc.) of the chemical species received at SurfaceEffect Dominant Sites 1430.

In a Transfer Electron Step 2250 an electron is transferred fromIntercalation Material 1610 to the charge carrier of Intercalate LithiumStep 2240. The electron is transferred in a faradaic reaction and istypically conducted from Substrate 105. The transfer occurs while thecharge carrier is within Intercalation Material 1610 and occurs at thepotential of that location. A reaction potential of the electrontransfer may be dependent on the reaction potential of the chargecarrier and the reaction potential of the Intercalation Material 1610.The potential of this conduction band can be influenced by both theIntercalation Material 1610 and nearby Surface Effect Dominant Sites1430. Surface Dominant Sites 1430 can catalyze transfer of lithium fromElectrolyte 125 to Intercalation Material 1610. As discussed elsewhereherein, this transfer can occur via an intermediate oxide such as Li₂O.The work function of this electron transfer can be different than thework function of the electron transfer in Transfer Electron Step 2230.For example, in various embodiments the work function is at least 0.001,0.1, 0.3, 0.4, 0.5, 0.8, 1.0, 1.3, 1.7, 2.0 or 2.4V, or any combinationthere between. In some embodiments it is thermodynamically morefavorable for lithium to be intercalated into Intercalation Material1610 than into the bulk of nanoparticles that include the Surface EffectDominant Sites 1430. However, the presence of the Surface EffectDominant Sites 1430 can catalyze intercalation of a charge carrier intoIntercalation Material 1610.

If the charge carrier is converted to an oxide in Transfer Electron Step2230 then, in some embodiments, Transfer Electron Step 2250 includetransfer of an oxygen back from Intercalation Material 1610 back toSurface Effect Dominant Sites 1430. This oxygen received atIntercalation Material 1610 as the oxide of the charge carrier, and isreleased from the charge carrier during intercalation. After beingtransferred back to Surface Effect Dominant Sites 1430, this oxygen canthen be used in further occurrences of Transfer Electron Step 2230,i.e., the oxygen is recycled.

While the description of FIG. 22 above assumes that the charge carrierreceived in Receive Lithium Step 2220 and the charge carrier IntercalateLithium Step 2240 are two different individual charge carriers (thatcould be of the same type), in various embodiments steps 2220, 2230 and2240 can be performed in by the same individual charge carriers. Forexample, in some embodiments, Receive Lithium Step 2220 includesreceiving a charge carrier at one of Surface Effect Dominant Sites 1430.Transfer Electron Step 2230 then includes a reaction in which the chargecarrier reacts with the Surface Effect Dominant Site 1430 to produce anintermediate compound. In some embodiment this reaction includes2Li⁺+MO+2e⁻→Li₂O +M (Where M is any of the transition metals discussedherein and Li₂O is the resulting intermediate compound). In IntercalateLithium Step 2240 the intermediate compound (e.g.. Li₂O) is intercalatedinto Intercalation Material 1610, or one (or both) of the Li in theintermediate compound are transferred from the O of Li₂O to an atom ofthe Intercalation material (e.g., Li_(x)Si). This transfer may result inregeneration of the MO that was split in Transfer Electron Step 2230.Note that in this example the same individual Li atom was involved ineach of the Steps 2220-2230 and 2240. Transfer Electron Step 2250 is notrequired in these embodiments of the methods illustrated by FIG. 22. Itis possible that in some embodiments both reaction sequences thatinclude an intermediate such as Li₂O and reaction sequences that do notinclude an intermediate occur during a single charging cycle.

Several embodiments are specifically illustrated and/or describedherein. However, it will be appreciated that modifications andvariations are covered by the above teachings and within the scope ofthe appended claims without departing from the spirit and intended scopethereof. For example, while the examples discussed herein have beenfocused on CNFs having a stacked-cone structure the teachings may beadapted to other materials having similar or alternative structures.Likewise, while a Cu substrate and Li charge carriers are discussedherein other substrates and charge carriers will be apparent to one ofordinary skill in the art. Silicon Layer 115 is optionally formed ofintercalation materials in addition to or as an alternative to silicon.For example, tin, germanium, carbon, graphite, graphene, silicon, othermaterials discussed herein or combinations thereof could be used asintercalation material. Additionally, aerogels, nano-wires, TiO₂(titanium oxide), metal wires, carbon wires, or boron nitridenano-fibers can be used in place of the carbon nano-fibers discussedherein. The relative concentrations of Binder 1440, Surface EffectDominant Sites 1430, Intercalation Material 1610 and CNF 110 and otherelements in the figures can vary significantly from that illustrated.

The electrodes taught herein may be included in a wide variety of energystorage devices including capacitors, batteries and hybrids thereof.These energy storage devices can be used in, for example, lightingsystems, portable electronics, load balancing devices, communicationdevices, backup power supplies, vehicles and computing devices. Theconcepts taught herein can be, in many cases, applied to cathodes aswell as anodes.

Details of VACNF Growth and Silicon Deposition, Microscopy andSpectroscopy Characterization, and Electrochemical Cell Assembly andCharge-Discharge Tests can be found in U.S. provisional application61/667,876 filed Jul. 3, 2012.

The embodiments discussed herein are illustrative of the presentinvention. As these embodiments of the present invention are describedwith reference to illustrations, various modifications or adaptations ofthe methods and or specific structures described may become apparent tothose skilled in the art. All such modifications, adaptations, orvariations that rely upon the teachings of the present invention, andthrough which these teachings have advanced the art, are considered tobe within the spirit and scope of the present invention. Hence, thesedescriptions and drawings should not be considered in a limiting sense,as it is understood that the present invention is in no way limited toonly the embodiments illustrated.

What is claimed is:
 1. An energy storage system comprising: a conductivesubstrate; a carbon nanofiber connected to the conductive substrate, thecarbon nanofiber including a plurality of exposed nanoscale edges alongthe length of the carbon nanofiber; and an intercalation materialconfigured to form a shell over at least part of the carbon nanofiber.2. The system of claim 1, wherein each of the exposed nanoscale edgesinclude edges of multiple graphitic sheets.
 3. The system of claim 1,wherein each of the exposed nanoscale edges is configured to controlgrowth of the intercalation material.
 4. The system of claim 1, whereineach of the exposed nanoscale edges is configured to provide a migrationpath for charge carriers to an interior of the carbon nanofiber.
 5. Thesystem of claim 1, wherein each of the exposed nanoscale edges includemultiple graphene edges.
 6. The system of claim 1, wherein theintercalation material is disposed in a feather-like structure along alength of the carbon nanofiber.
 7. The system of claim 1, wherein theintercalation material is configured such that expansion of theintercalation material is non-delaminating of the intercalation materialfrom the carbon nanofiber.
 8. The system of claim 1, further comprisingan electrolyte in contact with the intercalation material and includinga charge carrier.
 9. The system of claim 8, wherein the electrolyte is asolid electrolyte.
 10. The system of claim 8, wherein the charge carrierincludes lithium.
 11. The system of claim 8, further comprising acathode.
 12. The system of claim 1, wherein the carbon nanofiber is oneof a plurality of vertically aligned carbon nanofibers attached to thesubstrate.
 13. The system of claim 1, wherein the carbon nanofiber isdirectly attached to the conductive substrate.
 14. The system of claim1, wherein the carbon nanofiber is indirectly attached to the conductivesubstrate using a binder.
 15. The system of claim 1, wherein theintercalation layer includes silicon.
 16. The system of claim 1, furthercomprising a plurality of nanoparticles attached to the intercalationmaterial, each of the nanoparticles being configured to provide surfaceeffect dominant sites configured to adsorb charge carriers via faradaicinteractions on surfaces of the nanoparticles.
 17. An energy storagesystem comprising: a conductive substrate; a carbon nanofiber connectedto the conductive substrate, the carbon nanofiber including a pluralityof cup-like structures along the length of the carbon nanofiber; and anintercalation material configured to form a shell over at least part ofthe carbon nanofiber.
 18. The system of claim 17, wherein each of thecup-like structures includes walls having multiple graphitic sheets. 19.The system of claim 17, wherein each of the cup-like structures areconfigured to control growth of the intercalation material.
 20. Thesystem of claim 17, wherein the cup-like structures include spiral withcup-like cross-section.
 21. A method of producing an energy storagedevice, the method comprising: providing a conductive substrate; addingcarbon nanofibers to the conductive substrate, the carbon nanofiberseach including a plurality of exposed nanoscale edges along the lengthof the carbon nanofiber; and applying intercalation material to thecarbon nanofibers, the intercalation material being configured forintercalation of charge carriers.
 22. The method of claim 21, furthercomprising adding an electrolyte in contact with the intercalationmaterial and including a charge carrier.
 23. The method of claim 22,further comprising providing a cathode in contact with the electrolyte.24. The method of claim 21, wherein the carbon nanofibers are verticallyaligned carbon nanofibers attached to the substrate.
 25. The method ofclaim 21, wherein the carbon nanofibers are attached indirectly to theconductive substrate using a binder.
 26. A method of producing an energystorage device, the method comprising: providing a conductive substrate;adding carbon nanofibers to the conductive substrate, the carbonnanofibers each including a plurality of cup-like structures along thelength of the carbon nanofiber; and applying intercalation material tothe carbon nanofibers, the intercalation material being configured forintercalation of charge carriers.